EP2412688A1 - Concrete mixture comprising thermally inactivated cement-asbestos - Google Patents
Concrete mixture comprising thermally inactivated cement-asbestos Download PDFInfo
- Publication number
- EP2412688A1 EP2412688A1 EP20110171221 EP11171221A EP2412688A1 EP 2412688 A1 EP2412688 A1 EP 2412688A1 EP 20110171221 EP20110171221 EP 20110171221 EP 11171221 A EP11171221 A EP 11171221A EP 2412688 A1 EP2412688 A1 EP 2412688A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- asbestos
- cement
- weight
- comprised
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010425 asbestos Substances 0.000 title claims abstract description 71
- 229910052895 riebeckite Inorganic materials 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000004567 concrete Substances 0.000 title claims abstract description 17
- 239000004568 cement Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 230000002779 inactivation Effects 0.000 claims abstract description 8
- 239000004576 sand Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 230000035515 penetration Effects 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 230000009466 transformation Effects 0.000 description 19
- 238000010304 firing Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052634 enstatite Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 229910052612 amphibole Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052620 chrysotile Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 230000009972 noncorrosive effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011150 reinforced concrete Substances 0.000 description 4
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 4
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052839 forsterite Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ULEFFCDROVNTRO-UHFFFAOYSA-N trimagnesium;disodium;dihydroxy(oxo)silane;iron(3+) Chemical compound [Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Fe+3].[Fe+3].O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O ULEFFCDROVNTRO-UHFFFAOYSA-N 0.000 description 2
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- 208000033116 Asbestos intoxication Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010027406 Mesothelioma Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910007270 Si2O6 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910052891 actinolite Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052885 anthophyllite Inorganic materials 0.000 description 1
- 206010003441 asbestosis Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001678 gehlenite Inorganic materials 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 230000001459 mortal effect Effects 0.000 description 1
- 239000010852 non-hazardous waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000007853 structural degeneration Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052889 tremolite Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0475—Waste asbestos
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/246—Cements from oil shales, residues or waste other than slag from waste building materials, e.g. waste asbestos-cement products, demolition waste
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the invention relates to a concrete mixture comprising thermally inactivated asbestos cement.
- the commercial name asbestos indicates the minerals belonging to the asbestos family, silicates in the form of asbestos-fibre aggregates.
- the following minerals are covered by the definition of asbestos according to the Italian standards: chrysotile (serpentine asbestos), tremolite, actinolite, anthophyllite, amosite and crocidolite (amphibole asbestos).
- the crystalline fibrous asbestos form that determines the exceptional technological properties of asbestos is unfortunately also the cause of the proven toxicity of asbestos.
- the extremely fine fibres (they are nanometric in diameter and micrometric in length) can be both free/slightly bound and tightly bound.
- landfill sites show themselves to be possible sources of emissions because, if the packs of slabs of materials containing asbestos are possibly damaged and shattered when they are deposited, they may release fibres that concentrate in the air. Over the long term (over 10 years), the problem remains. It is considered that on a landfill site, over the long period, there is no coating system, however well designed and built, that can prevent all filtration leaks. Factors that determine the formation of open discontinuities that may allow unaltered leached material to escape over many kilometres are fissuring through drying and differential subsidence. The leached material may contain suspended particles even in large quantities. If these particles are not filtered, they enter the phreatic zone of the land, mix and move with the groundwater.
- the main transformations that occur at high temperature in materials containing asbestos can be classified as deoxidation and recrystallisation in solid state.
- the thermal treatment of chrysotile, the main component of the asbestos cement shows that at about 800 °C a transformation in solid state begins that leads to the complete recrystallisation in magnesium silicate (forsterite and enstatite) phases: Mg 3 (OH) 4 Si 2 O 5 ⁇ Mg 2 SiO 4 (forsterite) + MgSiO 3 (enstatite) + 2H 2 O
- amphibole crocidolite asbestos can be present as a secondary phase in the asbestos cement. If this hazardous mineral is treated thermally at temperatures above 1050 °C, after deoxidation, it shows a complex crystallisation sequence, with oxidation of bivalent iron: Na 2 MgFe" 2 Fe"' 2 Si 8 O 22 (OH) 2 ⁇ 2NaFe"'Si 2 O 6 (alkaline pyroxene) + MgSiO 3 (enstatite) + Fe 2 O 3 (haematite) + 3SiO 2 (cristobalite) + H 2 O
- the thermal transformation (recrystallisation) of the fibrous mineral also leads to the definitive elimination of the potential danger of these materials.
- Recently, the use of secondary raw material deriving from the thermal transformation of asbestos was permitted. This opens a new road for the definitive solution of the problem of asbestos inasmuch as it enables inactivation plants to be made that are able to ensure the total reliability of the effective transformation of asbestos cement in an inert and recyclable compound.
- the thermal transformation product is recyclable as a secondary raw material, according to recent directives of the European Union, provided that it does not contain asbestos and/or substances classified as category 1 or 2 cancerogenous substances in a total concentration above 0.1%. From IT0001368771 an innovative industrial process for the definitive solution of the asbestos problem is known.
- the process which is unique in the world in terms of type of thermal treatment and technological properties, is based on the chemical-crystalline conversion of waste containing asbestos. This permits the direct thermal transformation of slabs of asbestos cement, friable asbestos and/or glass/rock wool sealed in packages of plastics, deriving from normal reclamation and removal operations.
- the process of direct thermal transformation of the entire package is possible owing to a continuous industrial tunnel kiln.
- One of the particularities of the process is that it does not involve handling and/or grinding sealed packages of asbestos before firing.
- the industrial kiln ensures complete isolation of the material being fired from the external environment and is provided with a post-combustion system, through which all the fumes deriving from the process of transforming the waste and the package have to pass.
- the fumes coming from the after-burner are cooled and further have to pass through a double system of absolute HEPA filters and a scrubber.
- non-inactivated raw asbestos cement it is possible to directly use non-inactivated raw asbestos cement to prepare concrete by adding the asbestos cement directly to the mixture of natural raw materials and which are not intended for the production of clinker (production of clinker at 1350-1400 °C).
- the use of non-inactivated asbestos cement to produce concrete includes the risk of dispersion of asbestos in the environment, in the event of degradation of the concrete products in which the non-inactivated asbestos cement has been used.
- the object of the present invention is to make it possible to use asbestos cement without risks to make concrete.
- the object of the present invention is achieved with the use of secondary raw material produced by the thermal transformation (inactivation) of slabs of asbestos cement to produce concrete, according to claim 1.
- the secondary raw material produced by the thermal transformation (inactivation) of slabs of asbestos cement to obtain a concrete mixture having properties of resistance to compression, resistance to flexure and penetration depth of the water, which, on the basis of current legislation, makes the secondary raw material suitable for being used interiors of buildings with low humidity, for non-reinforced concrete products sunken into a non-corrosive ground or into non-corrosive water, for non-reinforced concrete products subject to wet-dry cycles but not subject to abrasion, ice or chemical attack, for parts of structures containing liquids, for foundations of buildings.
- the use of said secondary raw material further eliminates any risk of dispersion of asbestos into the environment.
- the secondary raw material that is usable according to the present invention is produced following thermal transformation of slabs of asbestos cement in both continuous and discontinuous industrial kilns operating in rapid cycles (firing time below 2 h, including the ascent ramp to firing temperature, isothermal phase at the firing temperature, and cooling) or slow (total firing time between 2 and 50 h, including the ascent ramp to the firing temperature, isothermal phase at the firing temperature, and cooling).
- the maximum treatment temperature must be comprised between 1050 and 1300 °C in such a manner as to obtain the complete transformation of the asbestos phases (both serpentine asbestos and amphibole asbestos) into silicate calcium, aluminium and magnesium phases (such as, for example, larnite 2CaO•SiO 2 , gehlenite Ca 2 Al(AlSi)O 7 , merwinite Ca 3 Mg(SiO 4 ) 2 , ferrite 4CaO•Al 2 O 3 •Fe 2 O 3 and/or into an amorphous phase based on Ca, Mg, Fe, Al, Si and oxygen).
- the asbestos phases both serpentine asbestos and amphibole asbestos
- silicate calcium, aluminium and magnesium phases such as, for example, larnite 2CaO•SiO 2 , gehlenite Ca 2 Al(AlSi)O 7 , merwinite Ca 3 Mg(SiO 4 ) 2 , ferrite 4CaO•Al 2 O 3 •Fe
- the secondary raw material is recycled in a percentage comprised between 1 and 20 % replacing commercial clinker to formulate concrete mixtures.
- the concrete mixture according to the invention containing the secondary raw material produced by thermal transformation (inactivation) of slabs of asbestos cement is usable according to current legislation to make:
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
- The invention relates to a concrete mixture comprising thermally inactivated asbestos cement.
- The commercial name asbestos indicates the minerals belonging to the asbestos family, silicates in the form of asbestos-fibre aggregates. The following minerals are covered by the definition of asbestos according to the Italian standards: chrysotile (serpentine asbestos), tremolite, actinolite, anthophyllite, amosite and crocidolite (amphibole asbestos). The crystalline fibrous asbestos form that determines the exceptional technological properties of asbestos is unfortunately also the cause of the proven toxicity of asbestos. The extremely fine fibres (they are nanometric in diameter and micrometric in length) can be both free/slightly bound and tightly bound. In the former case we talk of asbestos in friable matrix, for example sprayed asbestos or asbestos in flakes (flaked), but in the latter case we talk of asbestos in compact matrix, asbestos cement (known by the commercial name Eternit) being the most famous representative. Human activities, smog, acid rains, the temperature variations, UV rays, the action of wind, vibrations, both single and combined, cause erosion of the encasing matrix that favours the release of asbestos fibres. If dispersed in the air, the fibres can be inhaled and may reach the lungs where, even after very long incubation periods, they may cause diseases that are nearly always mortal. It is, today, in fact scientifically proved that inhaling asbestos fibres can severely damage the respiratory tract and develops asbestosis, mesothelioma or pulmonary carcinoma. At present, no scientific study exists that defines the minimum level of exposure to the fibres that is necessary for triggering an asbestos-related disease. This means that, at least theoretically, inhaling just a few fibres (environmental exposure) may be extremely hazardous. For these reasons, the extraction, import, export, marketing and production of asbestos, asbestos products or products containing asbestos are forbidden by law in many countries, for example Italy since 1992. Although materials containing asbestos have been banned, in Italia, for 18 years, there are still today about 2 billion square metres of asbestos concrete covering in Italy, 300 million square metres of friable asbestos and about 150 million square metres of products of various types such as joints, brake linings and clutches.
- In order to address this real emergency, making safe sites with products containing deteriorated asbestos has become a legal obligation. The most common method for making the covers safe is to remove the slabs, combined with disposal in a controlled landfill site for hazardous waste or for non-hazardous waste with a dedicated cell. In Italy, the landfill sites that can receive this type of waste are very few and public or private bodies encounter great resistance to the opening of new landfill sites. This is because there is scientific proof that a site for the disposal of waste containing asbestos is not a completely closed system, or at least is completely closed only over the medium term (1-10 years). If it is considered that the phases of the asbestos at ambient temperature can persist for a very long time, this may be a serious problem. Over the short term, landfill sites show themselves to be possible sources of emissions because, if the packs of slabs of materials containing asbestos are possibly damaged and shattered when they are deposited, they may release fibres that concentrate in the air. Over the long term (over 10 years), the problem remains. It is considered that on a landfill site, over the long period, there is no coating system, however well designed and built, that can prevent all filtration leaks. Factors that determine the formation of open discontinuities that may allow unaltered leached material to escape over many kilometres are fissuring through drying and differential subsidence. The leached material may contain suspended particles even in large quantities. If these particles are not filtered, they enter the phreatic zone of the land, mix and move with the groundwater. As asbestos is virtually indestructible at ambient temperature, it can concentrate in the percolate and, if it is not filtered, can reach the groundwater. Analyses conducted on the percolates of landfill sites in which items containing asbestos were deposited have established a significant number of asbestos fibres in said percolates. This situation is due to the structural degeneration of the packaging that contain the waste, caused by wear over time and by the conditions of deterioration that occur in the body of the landfill site after burying. Asbestos in water is in itself harmless but following evaporation can be concentrated on the surface ground and atmospheric agents (mainly wind) can make the asbestos return to be dispersed in the air. Modern technologies today provide a definitive, alternative solution to burial in landfill sites. In fact, it is proven that via thermal, mechanical or chemical treatment it is possible to transform and destroy asbestos fibres. The thermal transformation (complete destruction of the crystal lattice) is achieved by the action of the heat that enables the fibrous asbestos to be transformed into other silicates that are non-fibrous and harmless to human health.
- The main transformations that occur at high temperature in materials containing asbestos can be classified as deoxidation and recrystallisation in solid state. The thermal treatment of chrysotile, the main component of the asbestos cement, shows that at about 800 °C a transformation in solid state begins that leads to the complete recrystallisation in magnesium silicate (forsterite and enstatite) phases:
Mg3(OH)4Si2O5 ⇒ Mg2SiO4 (forsterite) + MgSiO3 (enstatite) + 2H2O
- Owing to this transformation, the chrysotile no longer exists as a mineralogical entity. The original chemical and physical properties of the transformed material are lost and it is consequently no longer dangerous.
- In addition to the chrysotile, amphibole crocidolite asbestos can be present as a secondary phase in the asbestos cement. If this hazardous mineral is treated thermally at temperatures above 1050 °C, after deoxidation, it shows a complex crystallisation sequence, with oxidation of bivalent iron:
Na2MgFe"2Fe"'2Si8O22(OH)2 ⇒ 2NaFe"'Si2O6 (alkaline pyroxene) + MgSiO3 (enstatite) + Fe2O3 (haematite) + 3SiO2 (cristobalite) + H2O
- The specific literature, clearly shows that asbestos as such or present in compact materials (asbestos cement), if properly heated, modifies the crystalline system and loses the asbestos fibre cladding through transformation into other non-fibrous and inert silicates.
- The thermal transformation (recrystallisation) of the fibrous mineral also leads to the definitive elimination of the potential danger of these materials. Recently, the use of secondary raw material deriving from the thermal transformation of asbestos was permitted. This opens a new road for the definitive solution of the problem of asbestos inasmuch as it enables inactivation plants to be made that are able to ensure the total reliability of the effective transformation of asbestos cement in an inert and recyclable compound. The thermal transformation product is recyclable as a secondary raw material, according to recent directives of the European Union, provided that it does not contain asbestos and/or substances classified as category 1 or 2 cancerogenous substances in a total concentration above 0.1%. From
IT0001368771 - It is further known from
IT0001256029 - The object of the present invention is to make it possible to use asbestos cement without risks to make concrete.
- The object of the present invention is achieved with the use of secondary raw material produced by the thermal transformation (inactivation) of slabs of asbestos cement to produce concrete, according to claim 1.
- Owing to the invention, it is possible to use the secondary raw material produced by the thermal transformation (inactivation) of slabs of asbestos cement to obtain a concrete mixture having properties of resistance to compression, resistance to flexure and penetration depth of the water, which, on the basis of current legislation, makes the secondary raw material suitable for being used interiors of buildings with low humidity, for non-reinforced concrete products sunken into a non-corrosive ground or into non-corrosive water, for non-reinforced concrete products subject to wet-dry cycles but not subject to abrasion, ice or chemical attack, for parts of structures containing liquids, for foundations of buildings.
- The use of said secondary raw material further eliminates any risk of dispersion of asbestos into the environment.
- An example of implementation of the invention is disclosed below merely by way of non-limiting example.
- The secondary raw material that is usable according to the present invention is produced following thermal transformation of slabs of asbestos cement in both continuous and discontinuous industrial kilns operating in rapid cycles (firing time below 2 h, including the ascent ramp to firing temperature, isothermal phase at the firing temperature, and cooling) or slow (total firing time between 2 and 50 h, including the ascent ramp to the firing temperature, isothermal phase at the firing temperature, and cooling). The maximum treatment temperature must be comprised between 1050 and 1300 °C in such a manner as to obtain the complete transformation of the asbestos phases (both serpentine asbestos and amphibole asbestos) into silicate calcium, aluminium and magnesium phases (such as, for example, larnite 2CaO•SiO2, gehlenite Ca2Al(AlSi)O7, merwinite Ca3Mg(SiO4)2, ferrite 4CaO•Al2O3•Fe2O3 and/or into an amorphous phase based on Ca, Mg, Fe, Al, Si and oxygen).
- The average chemical composition of the secondary raw material obtained with the aforesaid thermal treatment, expressed as a weight percentage of oxides of the main elements is as follows:
SiO2 = 25-40% Al2O3 = 2-8% Fe2O3 = 0-5% TiO2 = 0-2% CaO = 35-60% MgO = 2-10% Na2O = 0-3% K2O = 0-3% - The secondary raw material is recycled in a percentage comprised between 1 and 20 % replacing commercial clinker to formulate concrete mixtures.
- The average chemical composition of commercial clinker expressed as a weight percentage of oxides of the main elements is as follows:
SiO2 = 15-30% Al2O3 = 2-10% Fe2O3 = 0-6% TiO2 = 0-2% CaO = 45-68% MgO = 0-5% Na2O = 0-3% K2O = 0-3% - The concrete mixture according to the invention consists of cement binder in a fraction comprised between 14 and 18% and inert (sand + gravel) in a fraction comprised between 82 and 86% and water/cement binder ratio = 0.55-0.61. 80-99% of the cement binder consists of commercial clinker and 1-20% of the secondary raw material obtained from the thermal transformation (inactivation) of slabs of asbestos cement.
- In view of the technological properties of resistance to compression above 20 N/mm2, resistance to flexure above 2.5 N/mm2, and penetration depth of the water below 4 cm, the concrete mixture according to the invention containing the secondary raw material produced by thermal transformation (inactivation) of slabs of asbestos cement is usable according to current legislation to make:
- interiors of buildings with low humidity,
- non-reinforced concrete products sunken in non-corrosive ground or non-corrosive water,
- non-reinforced concrete products subject to wet-dry cycles and not subject to abrasion, ice or chemical attack;
- parts of structures containing liquid, foundations.
- The aforesaid values of resistance to compression, resistance to flexure and penetration depth of water, are measured in products made with the mixture according to the invention, after at least twenty-eight days from the manufacture of the products.
- The inventors of this patent application consider that this industrial application of the secondary raw material produced by thermal transformation (inactivation) of slabs of asbestos cement is an absolute innovation because it is not comprised in the prior art and is not clear from the prior art for those who are skilled in this field of research. The application can also be the object of immediate use in the industrial field.
Claims (5)
- Concrete mixture comprising cement binder in a quantity comprised between 14 and 18% in weight and inert materials, such as sand and gravel, in a quantity comprised between 82 and 86% in weight, characterised in that said cement binder comprises clinker in a quantity comprised between 80% and 99% in weight and secondary raw material obtained from the thermal inactivation of asbestos cement in a quantity comprised between 1% and 20% in weight and that the water/cement binder ratio is comprised between 0.55 and 0.61.
- Mixture according to claim 1, wherein the composition of said secondary raw material expressed as percentages in weight of oxides of the main components is as follows:
SiO2 = 25-40% Al2O3 = 2-8% Fe2O3 = 0-5% TiO2 = 0-2% CaO = 35-60% MgO = 2-10% Na2O = 0-3% K2O = 0-3% Volatile materials = 0-5%. - Mixture according to claim 1, or 2, wherein the composition of said clinker, expressed as percentages in weight of oxides of the main components is as follows:
SiO2 = 15-30% Al2O3 = 2-10% Fe2O3 = 0-6% TiO2 = 0-2% CaO = 45-68% MgO = 0-5% Na2O = 0-3% K2O = 0-3% Volatile materials = 0-10%. - Concrete mixture according to any preceding claim, characterised in that concrete products obtained with said mixture have, after at least twenty-eight days from manufacture thereof, the following properties:- resistance to compression greater than 20 N/mm2;- resistance to flexure greater than 2.5 N/mm2,- penetration depth of water less than 4 cm.
- Concrete mixture according to any preceding claim, wherein said secondary raw material is produced by thermal treatment of slabs of asbestos cement at a temperature comprised between 1050 and 1300°C, for a time comprised between 2 hours and 50 hours.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMO2010A000190A IT1400796B1 (en) | 2010-06-24 | 2010-06-24 | CONCRETE MIXTURE INCLUDING CEMENT-ASBESTOS THERMICALLY INERT |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2412688A1 true EP2412688A1 (en) | 2012-02-01 |
EP2412688B1 EP2412688B1 (en) | 2016-05-11 |
Family
ID=43735767
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11171221.2A Not-in-force EP2412688B1 (en) | 2010-06-24 | 2011-06-23 | Method for obtaining a concrete mixture comprising thermally inactivated cement-asbestos |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP2412688B1 (en) |
IT (1) | IT1400796B1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3196178A1 (en) * | 2016-01-22 | 2017-07-26 | Vykumny ustav stavebrich hmot, a.s. | Method for exploiting asbestos cement waste |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10759697B1 (en) | 2019-06-11 | 2020-09-01 | MSB Global, Inc. | Curable formulations for structural and non-structural applications |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1274665A (en) * | 1968-05-28 | 1972-05-17 | Nat Res Dev | Improvements in and relating to concrete mixes |
SU1296541A1 (en) * | 1984-12-18 | 1987-03-15 | Ростовский инженерно-строительный институт | Concrete mix for producing centrifuged articles |
EP0545850A1 (en) * | 1991-12-04 | 1993-06-09 | SOLVAY UMWELTCHEMIE GmbH | Use of asbestos decomposition wastes as aggregates for building materials |
DE4411324A1 (en) * | 1993-04-08 | 1995-09-28 | Witega Angewandte Werkstoff Forschung Gemeinnuetzige Gmbh Adlershof | Cement prodn. from asbestos cement or sprayed asbestos |
DE19517595A1 (en) * | 1995-05-08 | 1996-11-14 | Kokoschko Rene Dipl Krist | Treatment of asbestos fibre-cement binder combination materials |
EP1277527A1 (en) * | 2001-07-17 | 2003-01-22 | MVG, Mineralfaser-Verwertungs-Gesellschaft mbH | Method of converting asbestos-cement products into cement products |
JP2006342037A (en) * | 2005-06-10 | 2006-12-21 | Nozawa Corp | Method of recycling asbestos-containing building material |
WO2007048881A1 (en) * | 2005-10-25 | 2007-05-03 | Gypsmix Sarl | Granular composition comprising an anhydrite iii based hydraulic binder and a recycled asbestos-based compound |
-
2010
- 2010-06-24 IT ITMO2010A000190A patent/IT1400796B1/en active
-
2011
- 2011-06-23 EP EP11171221.2A patent/EP2412688B1/en not_active Not-in-force
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1274665A (en) * | 1968-05-28 | 1972-05-17 | Nat Res Dev | Improvements in and relating to concrete mixes |
SU1296541A1 (en) * | 1984-12-18 | 1987-03-15 | Ростовский инженерно-строительный институт | Concrete mix for producing centrifuged articles |
EP0545850A1 (en) * | 1991-12-04 | 1993-06-09 | SOLVAY UMWELTCHEMIE GmbH | Use of asbestos decomposition wastes as aggregates for building materials |
DE4411324A1 (en) * | 1993-04-08 | 1995-09-28 | Witega Angewandte Werkstoff Forschung Gemeinnuetzige Gmbh Adlershof | Cement prodn. from asbestos cement or sprayed asbestos |
DE19517595A1 (en) * | 1995-05-08 | 1996-11-14 | Kokoschko Rene Dipl Krist | Treatment of asbestos fibre-cement binder combination materials |
EP1277527A1 (en) * | 2001-07-17 | 2003-01-22 | MVG, Mineralfaser-Verwertungs-Gesellschaft mbH | Method of converting asbestos-cement products into cement products |
JP2006342037A (en) * | 2005-06-10 | 2006-12-21 | Nozawa Corp | Method of recycling asbestos-containing building material |
WO2007048881A1 (en) * | 2005-10-25 | 2007-05-03 | Gypsmix Sarl | Granular composition comprising an anhydrite iii based hydraulic binder and a recycled asbestos-based compound |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 198740, Derwent World Patents Index; AN 1987-283633, XP002629662, SHURYGIN, V.P.; ET AL: "concrete mix for producing centrifuged articles" * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3196178A1 (en) * | 2016-01-22 | 2017-07-26 | Vykumny ustav stavebrich hmot, a.s. | Method for exploiting asbestos cement waste |
Also Published As
Publication number | Publication date |
---|---|
ITMO20100190A1 (en) | 2011-12-25 |
EP2412688B1 (en) | 2016-05-11 |
IT1400796B1 (en) | 2013-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Spasiano et al. | Treatments of asbestos containing wastes | |
Rincón et al. | Recycling of inorganic waste in monolithic and cellular glass‐based materials for structural and functional applications | |
Paolini et al. | Asbestos treatment technologies | |
Tantawy et al. | Evaluation of the pozzolanic activity of sewage sludge ash | |
JP5658270B2 (en) | Manufacturing method of lightweight construction materials using sludge waste | |
Nam et al. | Thermochemical destruction of asbestos-containing roofing slate and the feasibility of using recycled waste sulfuric acid | |
Gualtieri | Mineral fibre-based building materials and their health hazards | |
JP2008514416A (en) | Use of coal ash to safely treat inorganic waste | |
AU2012278447B2 (en) | Method for manufacturing light-weight construction material using waste product and light-weight construction material manufactured thereby | |
KR102308067B1 (en) | Eco-friendly material composite concrete block and its manufacturing method | |
Li et al. | Solidification/stabilization of lead‐contaminated soil using cement and waste phosphorus slag | |
US5170728A (en) | Process and furnace for treating fusible waste | |
EP2412688B1 (en) | Method for obtaining a concrete mixture comprising thermally inactivated cement-asbestos | |
Gualtieri | Recycling asbestos-containing material (ACM) from construction and demolition waste (CDW) | |
Gualtieri et al. | Human health hazards associated with asbestos in building materials | |
US20110101267A1 (en) | Acid treatment under low temperature and pressure of waste containing asbestos | |
JP2016023995A (en) | Method for immobilizing radioactive cesium in surface soil contaminated with radioactive cesium | |
EP3089829B1 (en) | Process for recycling asbestos-containing steel scrap | |
JP2009291730A (en) | Method for detoxifying solid waste containing asbestos | |
Piyaphanuwat et al. | Alkali‐activated composites of calcium carbide and black rice husk ash for immobilizing electroplating sludge | |
Min et al. | Melting treatment of waste asbestos using mixture of hydrogen and oxygen produced from water electrolysis | |
JP2013513540A (en) | Manufacturing method of lightweight construction materials using asbestos waste | |
WO2018127478A1 (en) | A process for treatment of fly ash | |
JP2007302482A (en) | Method for treating asbestos-containing inorganic waste material | |
JP5023300B2 (en) | Treatment method for inorganic waste |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20120725 |
|
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1166775 Country of ref document: HK |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B09B 3/00 20060101ALI20150717BHEP Ipc: C04B 14/40 20060101ALI20150717BHEP Ipc: C04B 28/02 20060101AFI20150717BHEP Ipc: C04B 7/24 20060101ALI20150717BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20151002 |
|
INTG | Intention to grant announced |
Effective date: 20151127 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 798532 Country of ref document: AT Kind code of ref document: T Effective date: 20160515 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602011026340 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: FIAMMENGHI-FIAMMENGHI, CH |
|
REG | Reference to a national code |
Ref country code: RO Ref legal event code: EPE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160811 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 798532 Country of ref document: AT Kind code of ref document: T Effective date: 20160511 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160912 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160812 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160630 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602011026340 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20170228 |
|
26N | No opposition filed |
Effective date: 20170214 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160811 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160711 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160623 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20170524 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160811 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20170522 Year of fee payment: 7 Ref country code: RO Payment date: 20170609 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20110623 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160630 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160623 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160511 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602011026340 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1166775 Country of ref document: HK |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20180701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180623 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20210702 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220630 |